Antibacterial Activity Potential of Industrial Food Production Waste Extracts against Pathogenic Bacteria: Comparative Analysis and Characterization.

The Food and Agricultural Organization estimates a 17% loss in the food production chain, making it imperative to adopt scientific and technological approaches to address this issue for sustainability. Industrial food production waste and its value-added applications, particularly in relation to a wide variety of pathogenic microorganisms and the health-related effects have not been thoroughly investigated. This study explores the potential of food production waste extracts-lemon peel (LP), hot trub (HT), and coffee silverskin (CSS) as sources of bioactive compounds. Extraction was conducted using hydro-methanolic extraction with yields in LP (482 mg/1 g) > HT (332 mg/1 g) > CSS (20 mg/1 g). The agar diffusion assay revealed the substantial antibacterial activity of all three extracts against Erwinia Amylovora, Escherichia coli, Bacillus subtilis, and Bacillus aquimaris. All extracts demonstrated activity against Gram-positive and Gram-negative bacteria, displaying minimum inhibitory concentrations effective against pathogenic bacteria like Listeria monocytogenes, Staphylococcus aureus, Vibrio parahaemolyticus, and Salmonella enterica. Total phenolic content (TPC in mg GAE/1g) was 100, 20, and 100 for CSS, HT, and LP, respectively. Antioxidant activity by ABTS indicated IC50 of 3.09, 13.09, and 2.61 for LP, HT, and CSS, respectively. Also, the antioxidant activity of the extracts was further confirmed by DPPH assay with the best activity in CSS (9.84 GAEg-1) and LP (9.77 mg of GAEg-1) rather than in HT (1.45 GAEg-1). No adverse cytotoxic effects on HaCaT cells were observed. Pancreatic amylase inhibition demonstrated antidiabetic potential, with LP showing the highest levels (92%). LC-MS characterization identified polyphenols as the main compounds in CSS, prenylated compounds in HT, and flavanols in LP. The findings imply the potential sustainable use of food production waste in industry.

Identification of oxygenated triacylglycerols in pistachio nuts' lipids by reverse-phase high-resolution-liquid chromatography-ESI mass spectrometry.

Hydroxy- and peroxy-triacylglycerols are common products of lipid peroxidation formed during oil storage or heating or as enzymatic oxidation product of arachidonic acid as signaling molecules in mammals. In this study, oxygenated triacylglycerides (TAG) were identified in pistachio oil based on reverse phase(RP), high-performance liquid chromatography coupled with electrospray ionization and mass spectrometry (HPLC- ESI -MS). 20 novel lipid plant metabolites, classified based on their fragment spectra into a hydroxy (TAG-OH), an epoxy (TAG-O), and hydroperoxide (TAG-OOH) groups. We believe that this class of compounds has been for the first time observed as genuine secondary plant metabolites in a natural source in this case pistachio lipids of dietary relevance.

Metabolomic profiling and quantification of polyphenols from leaves of seven Acacia species by UHPLC-QTOF-ESI-MS.

The genus Acacia (Fabaceae) comprises >1350 species and has been used in traditional medicine as infusions and decoctions to treat wounds, sores, headaches, diarrhea, and cough. The leaf methanolic extracts of seven Acacia species growing in Egypt namely: Acacia saligna, Acacia seyal, Acacia xanthophloea, Acacia tortilis subsp. raddiana., Acacia tortilis, Acacia laeta, Acacia albida were analyzed using UPLC-QTOF-ESI-MS. A total of 37 polyphenols were identified and discussed in detail. They included phenolic acids, flavonoids, and procyanidins, among which sixteen polyphenols were identified in Acacia for the first time. Folin-ciocalteau assay and ferric reducing antioxidant power, cupric reducing antioxidant capacity, 2,20 -azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) cation radical and the scavenging capacity against 2,2-diphenyl-1- picrylhydrazyl radical were performed to investigate the total phenolic content and the antioxidant activity of the Acacia extracts, respectively. Furthermore, the absolute quantification of eighteen polyphenols common to most of the species was performed using UPLC-MS. It was evident that the differences in the chemical composition among the species accounted for the difference in antioxidant activity which was in line together with the total phenolic content.

Diterpenes stability of commercial blends of roasted and ground coffees packed in copolymer coupled with aluminium and eco-friendly capsules.

Diterpenes are group of compounds of the terpenic fraction of roasted coffee and account for about 7-20 % (w/w) of the lipid fraction. Several parameters can influence their occurrence in coffee beans and beverages including species and post-harvest processing. Diterpenes in coffee have been studied extensively, but to the best of the authors' knowledge, there is no information in the literature on their stability over time. Coffee is a relatively stable product under optimal temperature, humidity and oxygen conditions. However, during storage it can undergo a series of chemical and physical reactions that alter its flavour and lead to rancidity, mainly due to the oxidative reactions that take place on the lipid fraction. In this study, the effect of long-term storage on the diterpene content of different commercial coffee blends and packaging is analysed and critically discussed. The Results show that the storage influences the internal environment of the capsules with an increase in moisture and a decrease in pH favouring more reactive conditions, especially for Eco capsules. Relative stability over time is observed for cafestol and kahweol. dehydro derivatives show a degradation up to T60 independently on the blends and packaging, which is not related to their precursors. The permeability of packaging and blends affect the modification of these components: while a drastic oxidation process takes place in Arabica eco compatible capsules (PC) when acidity and moisture increase, in Arabica/Robusta eco compatible capsules (IC) as well as in Arabica/Robusta and Arabica standard capsules (IS and PS) the peroxides tend to increase resulting in an autocatalytic propagation.

Understanding the fragmentation of glucose in mass spectrometry.

The fragmentation mechanism of D-glucose was investigated in detail by two different fragmentation techniques, namely, collision-induced dissociation (CID) and infrared multiphoton dissociation (IRMPD) using all six 13 C-labeled isotopomers and 2 H-labeled isotopomers. For both CID and IRMPD energy-resolved measurements were carried out. Individual fragmentation pathways were studied at MS2 and MS3 levels. Additionally, we have developed an HPLC-tandem MS method to separate the anomers of D-glucose using a HILIC column and investigated their fragmentation patterns individually. We propose a complete fragmentation landscape of D-glucose, demonstrating that a rather simple multifunctional molecule displays extreme complexity in gas phase dissociation, following multiple parallel fragmentation routes yielding a total of 23 distinct fragment ions. The results allowed a detailed formulation of the complex fragmentation mechanism of D-glucose. The results have immediate consequences for the full structure analysis of complex carbohydrates.

Unbiased and biased chemometric analysis of LC-MS data from human urine following coffee intake.

We carried out a human volunteer study with 14 participants, eight of whom were asked to consume one cup of coffee at four different time points. Urine samples were collected at eight time points and analyzed by HPLC-MS analysis. The LC-MS data were subjected to unsupervised multivariate statistical analysis (principal component analysis) followed by supervised multivariate analysis (linear discriminant analysis). In an unbiased approach, in the absence of data preselection and filtering, the most important features explaining differences between coffee consumers and the control group observed showed variations in endogenous human hormonal steroid metabolites as well as xanthine derivatives. Only after a biased data treatment data revealed differences between the sample groups based on literature reported chlorogenic acid metabolites resulting directly from coffee intake. Such analysis could confirm the presence of 21 previously reported chlorogenic acid plasma metabolites as urinary metabolites. The application of tandem MS molecular networking revealed the presence of five bioavailable chlorogenic acid derivatives in urine previously not reported, including both quinic acid lactone and dimethoxy caffeoyl esters. Selected cinnamic acids were quantified in urine.

PtIV-Containing Hexaplatinate(II) [PtIVPtII6O6(AsO2(CH3)2)6]2- and Hexapalladate(II) [PtIVPdII6O6(AsO2(CH3)2)6]2.

The first PtIV-containing discrete polyoxoplatinate(II) [PtIVPtII6O6(AsO2(CH3)2)6]2- (Pt7) and polyoxopalladate(II) [PtIVPdII6O6(AsO2(CH3)2)6]2- (PtPd6) have been prepared and characterized in the solid state, in solution, and in the gas phase. The molecular structures of the noble metal-oxo clusters Pt7 and PtPd6 comprise a central, octahedral PtIVO6 hetero group surrounded by six square-planar MO4 (M = PtII, PdII) units, which are capped by six dimethylarsinate ligands. The polyanions were prepared under simple one-pot aqueous solution conditions by reacting H2Pt(OH)6 with either K2PtCl4 or Pd(NO3)2 in sodium dimethylarsinate buffer (pH 7) at 80 °C. Catalytic studies were performed on Pt7 supported on SBA15-apts for o-xylene hydrogenation at 300 °C and 90 bar H2 pressure and indicated excellent activity and recyclability with low activation temperature.

Rationalising the retro-Diels-Alder fragmentation pattern of viscutins using electrospray interface-tandem mass spectrometry coupled to theoretical modelling.

RATIONALE: Although mass spectrometry (MS) is a powerful tool in structural elucidation of unknown flavonoids based on their unique fragmentation patterns, proposing the correct fragmentation mechanism is still a challenge from tandem mass spectrometry data only. In recent years, computational tools such as molecular networking and MS2LDA have played a major role in the identification of structurally related compounds through an in-depth survey of their fragmentation patterns. METHODS: Therefore, in this study, three viscutin molecules in Viscum combreticola Engl. crude extracts were characterised using ultra-high-performance liquid chromatography-quadrupole-time-of-flight tandem mass spectrometry and MS2LDA, a computational tool. Ion-trap mass spectrometry and density functional theoretical modelling were used as confirmatory tools to rationalise the unique fragmentation patterns observed for these molecules. RESULTS: Here, MS2LDA revealed the presence of a unique Mass2Motif in all the three viscutin molecules at m/z 137, which was confirmed to be a 1,3 A- RDA (retro-Diels-Alder) fragmentation product using liquid chromatography-ion-trap mass spectrometry and density functional theoretical modelling. Moreover, MS2LDA proved to be useful in differentiating this spectral feature that was specific to viscutin molecules in the presence of other isobaric ions at m/z 137 occurring in compounds in other molecular families. CONCLUSION: Therefore, the results of the current study showed that computational tools such as MS2LDA are essential in uncovering some gas-phase fragmentation reactions of molecules in MS and that theoretical modelling is a powerful tool in rationalising these reactions in metabolite identification.

Mixed noble metal-oxo clusters: platinum(IV)-gold(III) oxoanion [PtIV2AuIII3O6((CH3)2AsO2)6].

The first discrete mixed platinum(IV)-gold(III) oxoanion [PtIV2AuIII3O6((CH3)2AsO2)6]- (1) was synthesized by reaction of H2Pt(OH)6 with H[AuCl4] in a simple one-pot procedure in aqueous solution at pH 7 and comprises two equivalent PtIVO6(As(CH3)2)3 units which are linked by three square-planar AuIIIO4 units. Polyanion 1 could be isolated as a potassium or sodium salt in good yield, which were structurally characterized in the solid state by single-crystal XRD and TGA, and in solution by multinuclear (1H, 13C, 195Pt) NMR, indicating that polyanion 1 is stable in solution, which was confirmed by ESI-MS studies. The sodium salt of 1 undergoes a clean single-crystal-to-single-crystal (SCSC) structural transformation upon rehydration and dehydration.

Mixed-valent palladium(IV/II)-oxoanion, [PdIVO6PdII6((CH3)2AsO2)6]2.

We report on the first example of a PdIV-containing polyoxopalladate(II). The discrete mixed-valent polyoxopalladate(IV/II), [PdIVPdII6O6((CH3)2AsO2)6]2-, comprising a central PdIV ion that is surrounded by a six-membered PdII-oxo ring capped by six dimethylarsinate groups, was synthesized and structurally characterized in the solid state, in solution and in the gas phase by multiple analytical techniques.

Discovery of Polythioplatinate(II) [Pt3S2(SO3)6]10- and Study of Its Solution and Catalytic Properties.

We have discovered the first polythioplatinate(II), [PtII3S2(SO3)6]10- (1), which was synthesized in aqueous basic medium (pH 11) by hydrothermal heating at 150 °C. Polyanion 1 comprises a discrete, triangular assembly of three Pt2+ ions linked by two µ3-sulfido ligands, and their square-planar coordination geometry is completed by two terminal S-bound sulfito ligands. Polyanion 1 was isolated as a hydrated sodium salt, Na10[PtII3(µ3-S)2(SO3)6]·22H2O (Na-1), which was characterized in the solid state by single-crystal X-ray diffraction, Fourier-transform infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectra, and elemental analysis, in solution by 195Pt NMR and atomic absorption spectroscopy, and in the gas phase by electrospray ionization mass spectrometry. Density functional theory calculations were performed, and the 195Pt NMR chemical shifts of 1 were computed theoretically and shown to match well with the experimental data. Furthermore, the discrete title polyanion 1 was immobilized on mesoporous SBA-15 support and used as a precatalyst for the hydrogenation of o-xylene.

Investigating the interaction between dietary polyphenols, the SARS CoV-2 spike protein and the ACE-2 receptor.

The global spread of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has called for an urgent need for the identification of compounds able to control, prevent or slow down the global pandemic. Several dietary polyphenols were assayed against binding to the SARS CoV-2 S1 spike protein and the human ACE-2 receptor, the target of the SARS CoV-2 virus using nano differential scanning fluorimetry, suggesting interaction of dietary polyphenols with both proteins. Following this initial screening the two dietary polyphenols with the strongest affinity were evaluated in a second functional binding assay. The assay was based on the thermophoresis of a fluorescently labelled spike protein and the ACE-2 receptor in the presence of dietary concentrations of the polyphenol in question. It could be experimentally shown that 5-caffeoyl quinic acid and epicatechin reduce the binding constant between SARS CoV-2 spike protein of the alpha variant and the ACE-2 receptor by a factor of ten. The finding could as well be applied to black tea and a coffee beverage with dietary 5-CQA concentrations for the alpha variant Spike protein. Hence it can be speculated that a cup of coffee reduces binding of the virus to its human target, therefore reducing the likelihood of infection with SARS CoV-2, acting as a virus entry-inhibitor.

LC-MS Characterization and Quantification of Known and Unknown (Poly)phenol Metabolites-Possible Pitfalls and Their Avoidance.

This review focuses on the LC-MS characterization and quantification of dietary (poly)phenols and their metabolites. It draws attention to errors, omissions, and misunderstandings that appear frequently in published papers, and suggests strategies for their avoidance. Aspects covered include the use of authentic standards and surrogate reference materials, the importance of collecting and archiving Total Ion Current MS data, the limitations of using on-line compilations of accurate mass MS data to assign unknown components when multiple isomers are possible, and the often understated magnitude of person-to-person variation that may significantly impact at population level any potential health benefit.

Discrete, Cationic Palladium(II)-Oxo Clusters via f-Metal Ion Incorporation and their Macrocyclic Host-Guest Interactions with Sulfonatocalixarenes.

We report on the discovery of the first two examples of cationic palladium(II)-oxo clusters (POCs) containing f-metal ions, [PdII6 O12 M8 {(CH3 )2 AsO2 }16 (H2 O)8 ]4+ (M=CeIV , ThIV ), and their physicochemical characterization in the solid state, in solution and in the gas phase. The molecular structure of the two novel POCs comprises an octahedral {Pd6 O12 }12- core that is capped by eight MIV ions, resulting in a cationic, cubic assembly {Pd6 O12 MIV8 }20+ , which is coordinated by a total of 16 terminal dimethylarsinate and eight water ligands, resulting in the mixed PdII -CeIV /ThIV oxo-clusters [PdII6 O12 M8 {(CH3 )2 AsO2 }16 (H2 O)8 ]4+ (M=Ce, Pd6 Ce8 ; Th, Pd6 Th8 ). We have also studied the formation of host-guest inclusion complexes of Pd6 Ce8 and Pd6 Th8 with anionic 4-sulfocalix[n]arenes (n=4, 6, 8), resulting in the first examples of discrete, enthalpically-driven supramolecular assemblies between large metal-oxo clusters and calixarene-based macrocycles. The POCs were also found to be useful as pre-catalysts for electrocatalytic CO2 -reduction and HCOOH-oxidation.

A Practitioner's Dilemma Mass Spectrometry-Based Annotation and Identification of Human Plasma and Urinary Polyphenol Metabolites.

The practitioner's dilemma in metabolite assignment can be described as follows: for compound and metabolite identification, strict guidelines should be followed using authentic standards only, or uncertainties in structure assignment of compounds with the certainty of consequential errors should be accepted. These uncertainties arise due to limitation of software and databases in combination with the complexity of the human body fluid samples.

Cocoa bean fingerprinting via correlation networks.

Cocoa products have a remarkable chemical and sensory complexity. However, in contrast to other fermentation processes in the food industry, cocoa bean fermentation is left essentially uncontrolled and is devoid of standardization. Questions of food authenticity and food quality are hence particularly challenging for cocoa. Here we provide an illustration how network science can support food fingerprinting and food authenticity research. Using a large dataset of 140 cocoa samples comprising three cocoa fermentation/processing stages and eight countries, we obtain correlation networks between the cocoa samples by computing measures of pairwise correlation from their liquid chromatography-mass spectrometry (LC-MS) profiles. We find that the topology of correlation networks derived from untargeted LC-MS profiles is indicative of the fermentation and processing stage as well as the origin country of cocoa samples. Progressively increasing the correlation threshold firstly reveals network clusters based on processing stage and later country-based clusters. We present both, qualitative and quantitative evidence through network visualization, network statistics and concepts from machine learning. In our view, this network-based approach for classifying mass spectrometry data has broad applicability beyond cocoa.

Lignin and Its Pathway-Associated Phytoalexins Modulate Plant Defense against Fungi.

Fungi infections cause approximately 60-70% yield loss through diseases such as rice blast, powdery mildew, Fusarium rot, downy mildew, etc. Plants naturally respond to these infections by eliciting an array of protective metabolites to confer physical or chemical protection. Among plant metabolites, lignin, a phenolic compound, thickens the middle lamella and the secondary cell walls of plants to curtail fungi infection. The biosynthesis of monolignols (lignin monomers) is regulated by genes whose transcript abundance significantly improves plant defense against fungi. The catalytic activities of lignin biosynthetic enzymes also contribute to the accumulation of other defense compounds. Recent advances focus on modifying the lignin pathway to enhance plant growth and defense against pathogens. This review presents an overview of monolignol regulatory genes and their contributions to fungi immunity, as reported over the last five years. This review expands the frontiers in lignin pathway engineering to enhance plant defense.

"Thermal Peroxidation" of Dietary Pentapeptides Yields N-Terminal 1,2-Dicarbonyls.

In this contribution we investigate the thermal degradation of dietary-relevant pentapeptides. Most unsaturated lipids degrade by the well-known peroxidation mechanism. Here we show a degradation mechanism of peptides analogous to lipid peroxidation, forming a series of novel degradation products with possible toxicological relevance. At elevated temperatures above 180°C, pentapeptides with an N-terminal phenylalanine moiety react via a debenzylation to form 1,2-dicabonyl compounds, replacing the N-terminal primary amine. We propose a radical-based reaction mechanism that leads via a common peroxoaminal intermediate to two distinct types of reaction products with a terminal α-1,2 diamide or an α-amide-aldehyde functionality.

LC-MS based metabolomic approach for the efficient identification and relative quantification of bioavailable cocoa phenolics in human urine.

This study was designed to investigate the rate and extent of urinary excretion of cocoa phenolic metabolites after human intake using metabolomics approach. In this context, a feeding trial was conducted where urine samples were collected at different time points over 48-h period. Several biomarkers were highlighted in LC-MS based chemometrics using principal component (PCA) and partial least squares discriminant analysis (PLS-DA), which revealed the presence of both epicatechin and gut microbial phenyl-γ-valerolactones (PVLs) conjugated analogues. The presences of these metabolites segregated and grouped the samples based on cocoa and non-cocoa ingestion. Furthermore, semi quantification of major bioavailable metabolites was performed to determine the interindividual differences and assess the relative bioavailability of cocoa compounds in the human body. Our approach presented here is unique in displaying a combination of LC-MS based chemometrics visualization strategies, which revealed and identified significant biomarkers that could reduce the problems associated with data screening complexity.